Modified thermal evaporation process using GeO2 for growing ZnO structures

In the current work, zinc oxide (ZnO) nano/microstructures are synthesized using a modified thermal-evaporation process by introducing germanium oxide (GeO₂) powder mixed with metallic Zn powder as the raw material. Without the use of any catalyst and oxygen flow in the furnace system, GeO₂ is utilized to provide an oxygen source for the growth of ZnO structure. The samples are treated by different temperatures ranging from 500 to 900 °C. Morphology, phase structure, and photoluminescence properties are investigated by scanning electron microscopy (SEM), X-ray diffractometer (XRD) and photoluminescence (PL) spectrometer. The structures and morphologies of the samples were found to vary with growth temperature. The XRD diffraction peaks show that the films grown at temperature from 600 to 800 °C consist of hexagonal wurtzite ZnO structures. Room-temperature PL measurement revealed ZnO spectra representing two bands: near-band-edge emission in the ultraviolet (UV) region and broad deep-level emission centered at about 500 nm. The strong UV emission in the PL spectra indicates that the GeO₂ supplies sufficient oxygen for formation of ZnO structures with few oxygen vacancies. The growth mechanism and the roles of GeO₂ for formation of ZnO structures are discussed in detail.     

Effect of substrate temperature on the morphology, structural and optical properties of Zn1−xCoxO thin films

Zn_1−xCo_xO thin films with c-axis preferred orientation were deposited on sapphire (0 0 0 1) by pulsed laser deposition (PLD) technique at different substrate temperatures in an oxygen-deficient ambient. The effect of substrate temperature on the microstructure, morphology and the optical properties of the Zn_1−xCo_xO thin films was studied by means of X-ray diffraction (XRD), atomic force microscopy (AFM), UV-visible-NIR spectrophotometer, fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted as substrate temperature rose. The structure of the samples was not distorted by the Co incorporating into ZnO lattice. The surface roughness of all samples decreased as substrate temperature increased. The Co concentration in the film was higher than in the target. Emission peak near band edge emission of ZnO from the PL spectra of the all samples was quenched because the dopant complexes acted as non-radiative centers. While three emission bands located at 409 nm (3.03 eV), 496 nm (2.5 eV) and 513 nm (2.4 eV) were, respectively, observed from the PL spectra of the four samples. The three emission bands were in relation to Zn interstitials, Zn vacancies and the complex of V_O and Zn_i (V_OZn_i). The quantity of the Zn interstitials maintained invariable basically, while the quantity of the V_OZn_i slightly decreased as substrate temperature increased.     

Transitions of microstructure and photoluminescence properties of the Ge/ZnO multilayer films in certain annealing temperature region

The Ge/ZnO multilayer films have been prepared by rf magnetron sputtering. The effects of annealing on the microstructure and photoluminescence properties of the multilayers have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectrometry and photoluminescence (PL) spectrometry. The investigation of structural properties indicates that Zn₂GeO₄ has been formed with (2 2 0) texture and Zn deficiency from Ge/ZnO multilayer films in the process of annealing. However, lower Zn/Ge ratio can be improved by annealing. The annealed multilayers show three main emission bands at 532, 700, and 761 nm, which originate from the transition between oxygen vacancy () and Zn vacancies (V_Zn), the radiative recombination of quantum-confined excitons (QCE) in Ge nanocrystals, and the optical transition in the GeO color centers, respectively. Finally, the fabrication of thin film Zn₂GeO₄ from Ge/ZnO multilayer films by annealing at low temperature provides another approach to prepare the green-emitting oxide phosphor film:Zn₂GeO₄:Mn.     

The electronic structure and photoluminescence properties of Ca2GeO4:Eu in ultraviolet and vacuum ultraviolet region

Ca₂GeO₄:Eu³⁺ phosphors were synthesized by the solid state method. The ultraviolet and vacuum ultraviolet excited photoluminescence properties were investigated in detail. It revealed that the emission of Ca₂GeO₄:Eu³⁺ comprised two parts: the red emission of Eu³⁺ and host defect emission in 330-550 nm. Ca₂GeO₄:Eu³⁺ presented intense excitation intensity at 163-200 and 466 nm, which suggested the potential applications in plasma display panels and light emitting diodes. The excitation spectra were studied to identify the photoluminescence mechanisms of Ca₂GeO₄:Eu³⁺. First principles calculation within the local density approximation of the density functional theory was applied to calculate the electronic structure and linear optical properties of Ca₂GeO₄.     

Study on the structure and optical property of Zn1−xCuxO sol–gel thin films on quartz substrate

Zn_1−xCu_xO thin films (x=0, 1.0, 3.0, 5.0%) are prepared on quartz substrate by sol–gel method. The structure and morphology of the samples are investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The results show that Cu ions were effectively penetrated into the ZnO crystal lattices with substitutional and interstitial impurities to form stable solid solutions without changing the polycrystalline wurtzite structure. Two peaks at 420 nm (2.95 eV, violet), 485 nm (2.56 eV, blue) have been observed from the photoluminescence (PL) spectra of the samples. It is concluded that the violet peak may correspond to the exciton emission; the blue emission corresponds to the electron transition from the bottom of the conduction band to the acceptor level of zinc vacancy. The optical test shows that the optical band gap E_g is decreased with the increase amount of Cu doping in ZnO. The band gap decrease from 3.40 eV to 3.25 eV gradually. It is also found that the transmission rate is increased rapidly with the increase of Cu ions concentration.     

Preparation and characterization of multi-functional CoFe2O4-ZnO nanocomposites

Multi-functional magnetic, photoluminescent and photocatalytic CoFe₂O₄-ZnO nanocomposites were successfully synthesized by a collosol method. The average diameter of the prepared CoFe₂O₄-ZnO nanocomposites was 30±5 nm, and a diffusion layer was formed to link CoFe₂O₄ and ZnO. The saturation magnetization of the CoFe₂O₄-ZnO nanocomposites was 8.99 emu/g. Generation of ZnO from Zn(OH)₂ collosol was nearly complete after thermal decomposition at about 380 °C. A photoluminescence emission peak was observed at 443 nm when excitated at 350 nm. Degradation of methyl orange is performed by CoFe₂O₄-ZnO nanocomposites under ultraviolet radiation, with a degradation rate of up to 93.9%.     

Preparation and characterization of Zn2SiO4: Mn phosphors with hydrothermal methods

Mn²⁺-doped Zn₂SiO₄ phosphors had been prepared by hydrothermal method in stainless-steel autoclaves. Effects of synthesized methods, reaction temperature, ambience of heat treatment on the structure and the luminescence properties of this silicate were studied with X-ray diffraction apparatus (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM) and fluorescence spectrum. Results show that Zn₂SiO₄ nanocrystalline can be obtained by hydrothermal method at relatively low temperatures. The absorption pattern shows an absorption edge at about 380 nm originated from ZnO crystals and two absorption bands at about 215 and 260 nm. Mn²⁺-doped Zn₂SiO₄ has a luminescence band with the wavelength at about 522 nm under 255 nm excitation, and the luminescent intensity increases after being heat treated.     

Optical and electrical properties of p-type ZnO fabricated by NH3 plasma post-treated ZnO thin films

In this paper, a simple method is reported to obtain nitrogen-doped p-ZnO film. In this method NH₃ plasma, generated in a plasma-enhanced chemical vapor deposition system, was employed to treat ZnO thin film. By Hall-effect measurement, a p-type conductivity was observed for the treated film with the hole density of 2.2 × 10¹⁶ cm⁻³. X-ray photoelectron spectroscopy (XPS) results confirmed that nitrogen was incorporated into ZnO film during the treatment process to occupy the oxygen positions. In low temperature photoluminescence spectra, an emission peak corresponding to acceptor-donor pair was observed. From this emission peak we calculated the N-related acceptor binding energy to be 130 meV.     

Surface characterization and luminescent properties of SrAl2O4:Eu,Dy nano thin films

SrAl₂O₄:Eu²⁺, Dy³⁺ thin films were grown on Si (1 0 0) substrates in different atmospheres using the pulsed laser deposition (PLD) technique. The effects of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological and photoluminescence (PL) properties of the films were investigated. The films were ablated using a 248 nm KrF excimer laser. Improved PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres compared to those prepared in vacuum. A stable green emission peak at 520 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions was obtained. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The diffusion of adventitious C into the nanostructured layers deposited in the Ar and O₂ atmospheres was most probably responsible for the quenching of the PL intensity after annealing.     

磁控共溅射法制备的Zn2GeO4多晶薄膜结构及其光致发光研究

用射频磁控共溅射方法在不同温度的单晶硅基片上生长薄膜,然后在800℃真空环境下对薄膜进行退火处理,成功获得了结晶状态良好的Zn₂GeO₄多晶薄膜.利用X射线衍射(XRD),X射线光电子能谱(XPS)和原子力显微镜(AFM)对薄膜进行了结构、成分和形貌分析,研究了基片温度对三者的影响. 结果显示,当基片温度升高到400℃以上时,薄膜中的Zn₂GeO₄晶粒在(220)方向上显示出了明显的择优取向. 当基片温度在500—600℃范围内,有利于GeO₂结晶相的形成. XPS显示薄膜中存在着Zn₂GeO₄,GeO₂,GeO,ZnO四种化合态. 同时,随着基片温度的升高,晶粒尺寸增大且薄膜表面趋于平整. 薄膜的光致发光在绿光带存在中心波长为530和550nm两个峰,应该归因于主体材料Zn₂GeO₄中两个不同的Ge²⁺的发光中心. 关键词： 射频磁控溅射 2GeO₄')" href="#">Zn₂GeO₄ 荧光体     

Structural,optical, FTIR and photoluminescence properties of Zn0.96−xCo0.04CuxO (x=0.03, 0.04 and 0.05) nanopowders

Un-hydrogenated and hydrogenated Cu, Co co-doped ZnO (Zn_0.96−xCo_0.04Cu_xO, x=0.03, 0.04 and 0.05) nanopowders have been synthesized by co-precipitation method. The synthesized samples have been characterized by powder X-ray diffraction, energy dispersive X-ray spectra, UV–Visible spectrophotometer and Fourier transform infrared spectroscopy. The calculated average crystalline size increases from 37.3 to 50.6 nm for un-hydrogenated samples from x=0.03 to 0.05 and it changes from 29.4 to 34.9 nm for hydrogenated samples. The change in lattice parameters, micro-strain, a small shift of X-ray diffraction peaks towards lower angles and reduction in energy gap reveal the substitution of Cu²⁺ ions into Zn–Co–O lattice. The hydrogenation effect reduces the particle size and induces the more uniform distribution of particles than the un-hydrogenated samples which is confirmed by SEM micrographs. Photoluminescence spectra of Zn_0.96−xCo_0.04Cu_xO system shows that red shift in near band edge ultraviolet emission from 393 to 403 nm with suppressing intensity and a blue shift in green band emission from 537 to 529 nm with enhancing intensity confirms the substitution of Cu into the Zn–Co–O lattice.     

Nano-star formation in Al-doped ZnO thin film deposited by dip-dry method and its characterization using atomic force microscopy, electron probe microscopy, photoluminescence and laser Raman spectroscopy

Zinc oxide doped with Al (AZO) thin films were prepared on borosilicate glass substrates by dip and dry technique using sodium zincate bath. Effects of doping on the structural and optical properties of ZnO film were investigated by XRD, EPMA, AFM, optical transmittance, PL and Raman spectroscopy. The band gap for ZnO:Al (5.0 at. wt.%) film was found to be 3.29 eV compared with 3.25 eV band gap for pure ZnO film. Doping with Al introduces aggregation of crystallites to form micro-size clusters affecting the smoothness of the film surface. Al³⁺ ion was found to promote chemisorption of oxygen into the film, which in turn affects the roughness of the sample. Six photoluminescence bands were observed at 390, 419, 449, 480, 525 and 574 nm in the emission spectra. Excitation spectra of ZnO film showed bands at 200, 217, 232 and 328 nm, whereas bands at 200, 235, 257 and 267 nm were observed for ZnO:Al film. On the basis of transitions from conduction band or deep donors (CB, Zn_i or V_OZn_i) to valence band and/or deep acceptor states (VB, V_Zn or O_i or O_Zn), a tentative model has been proposed to explain the PL spectra. Doping with Al³⁺ ions reduced the polar character of the film. This has been confirmed from laser Raman studies.     

Photoluminescence from ZnO-SiO2 opals with different sphere diameters and thicknesses

We systematically investigated the photoluminescence (PL) and transmittance characteristics of ZnO-SiO₂ opals with varied positions of the stop-band and film thicknesses. An improved ultraviolet (UV) luminescence was observed from ZnO-SiO₂ composites over pure ZnO nanocrystals under 325 nm He-Cd laser excitation at room temperature. The UV PL of ZnO nanocrystals in SiO₂ opals with stop-bands center of 410 nm is sensitive to the thickness of opal films, and the UV PL intensity increases with the film thickness increasing. The PL spectra of ZnO nanocrystals in SiO₂ opals with stop-bands center of 570 nm show a suppression of the weak visible band. The experimental results are discussed based on the scattering and/or absorbance in opal crystals.     

Prepare high efficiency Mn-doped Zn2SiO4 green phosphors in air using nano-particles

In this study, nano-scale precursors of ZnO, SiO₂, and MnO₂ powders were used to prepare mixtures with the compositions of 2ZnO+SiO₂+X mol% MnO₂ (X=MnO₂/2ZnO, abbreviated as Zn₂SiO₄-X-MnO₂), where 2≤X≤5. The mixed Zn₂SiO₄-X-MnO₂ mixtures were calcined from 900 to 1300 °C in air in order to synthesize Zn₂SiO₄:Mn²⁺ green phosphors. The X-ray diffraction patterns of Zn₂SiO₄-X-MnO₂ particles indicated that ZnO was present in the 900 °C-calcined Zn₂SiO₄-X-MnO₂ phosphors, but not in particles calcined at temperatures of 1000 °C and higher. However, the unapparent secondary phase of ZnMnO₃ was found in the 1200 and 1300 °C-calcined Zn₂SiO₄-5-MnO₂ compositions. The luminescent characteristics of Zn₂SiO₄-X-Mn²⁺ phosphors were compared with that of a commercial product (Nichia Corp., Japan). The photoluminescence (PL) intensity of 1200 °C-calcined Zn₂SiO₄-4-MnO₂ phosphors was higher and the decay times of all synthesized Zn₂SiO₄-X-MnO₂ phosphors were longer than those of the commercial product.     

Spherical Zn2SiO4:Eu@SiO2 phosphor particles in core-shell structure: Synthesis and characterization

Spherical SiO₂ particles have been coated with Zn₂SiO₄:Eu³⁺ phosphor layers by a Pechini sol-gel process. The microstructure and luminescent properties of the obtained Zn₂SiO₄:Eu³⁺@SiO₂ particles were well characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra, and lifetime. The results demonstrate that the Zn₂SiO₄:Eu³⁺@SiO₂ particles, which have regular and uniform spherical morphology, emitted an intensive red light emission at 613 nm under excitation at 395 nm. Besides, the effects of the Eu³⁺ concentration, annealing temperature and charge compensators of Li⁺ ions on the PL emission intensities were investigated in detail.     

Photoluminescence properties and effects of dopant concentration in Bi2ZnB2O7:Tb phosphor

A novel green phosphor, Tb³⁺ doped Bi₂ZnB₂O₇ was synthesized by conventional solid state reaction method. The phase of synthesized materials was determined using the XRD, DTA/TG and FTIR. The photoluminescence characteristics were investigated using spectrofluorometer at room temperature. Bi₂ZnB₂O₇:Tb³⁺ phosphors excited by 270 nm and 485 nm wavelengths. The emission spectra were composed of three bands, in which the dominated emission of green luminescence Bi₂ZnB₂O₇:Tb³⁺ attributed to the transition ⁵D₄ → ⁷F₅ is centered at 546 nm. The dependence of the emission intensity on the Tb³⁺ concentration for the Bi_2−xTb_xZnB₂O₇ (0.01 ≤ x ≤ 0.15) was studied and observed that the optimum concentration of Tb³⁺ in phosphor was 13 mol% for the highest emission intensity at 546 nm.     

The morphology and optical properties of Cr-doped ZnO films grown using the magnetron co-sputtering method

Undoped ZnO and Zn_0.9Cr_0.1O films were prepared on Al₂O₃ (0 0 0 1) substrates using the magnetron co-sputtering technique. X-ray diffraction scans show that all films exhibit nearly single-phase wurtzite structure with c-axis orientation. Both chromium doping and growth ambient have a significant impact on the lattice constants and nucleation processes in ZnO film. A large quantity of subgrains (10 nm in size) has been observed on Zn_0.9Cr_0.1O film grown under Ar + O₂, while irregular plateau-like grains 40-50 nm in size were observed on Zn_0.9Cr_0.1O film grown under Ar + N₂. The ultraviolet-visible transmittance and optical bandgap of all films were also examined. The photoluminescence spectra of all films exhibit a broad emission located around 400 nm, which is composed of one weak ultraviolet luminescence and another rather intense near-violet one, as determined by Gaussian peak fitting. The near-violet emission centered on 400 nm might originate from the electron transition between the band tail state levels of surface defects and/or lattice imperfection in the ZnO film.     

Synthesis and performance of core-shell structured ZnO/In2O3 composites in situ growth

Core-shell structured ZnO/In₂O₃ composites were successfully synthesized via situ growth method. Phase structure, morphology, microstructure and property of the products were investigated by X-ray diffraction (XRD), TG-DTA, field emission scanning electron microscopy (FESEM), energy-dispersive spectrometry (EDS), transmission electron microscope (TEM) and photoluminescence (PL). Results show that the core-shell structures consist of spindle-like ZnO with about 800 nm in length and 200 nm in diameter, and In₂O₃ particles with a diameter of 50 nm coated on the surface of ZnO uniformly. HMTA plays an important role in the formation of core-shell structures and the addition of In₂O₃ has a great effect on PL spectrum. Possible mechanism for the formation of core-shell structures is also proposed in this paper.     

A new self-activated yellow-emitting phosphor Zn2V2O7 for white LED

A new self-activated yellow-emitting Zn₂V₂O₇ phosphor was synthesized by high temperature solid-state reaction. X-ray powder diffraction (XRD) analysis confirmed the sample with monoclinic formation of Zn₂V₂O₇. The excitation and emission spectra indicated the phosphor can be efficiently excited by near ultraviolet (NUV) light in 220–400 nm range and exhibit a bright broad yellow emission with the highest emission intensity at 531 nm. The broad emission band from 400 to 650 nm can be attributed to the charge transfer transition in the VO₄ tetrahedra, which suggests that the phosphor is a promising yellow phosphor applied for white light-emitting diodes (WLED).     

L10 FePt thin films with [0 0 1] crystalline growth fabricated by SiO2 addition—rapid thermal annealing and dot patterning of the films

FePt films that have a high degree of order S in their L1₀ structure (S>0.90) and well-defined [0 0 1] crystalline growth perpendicular to the film plane were fabricated on thermally oxidized Si substrates by the addition of an oxide and successive rapid thermal annealing (RTA). The mechanism of L1₀ ordering and [0 0 1] crystalline growth perpendicular to the film plane arising through the oxide addition and RTA process is also discussed. The L1₀ ordering (S>0.90) and the [0 0 1] crystalline growth were achieved by (1) lowering the activation energy due to in-plane tensile stress and the initiation of L1₀ ordering at a low temperature, (2) [0 0 1] crystalline growth through in-plane tensile stress, and (3) enhancement of atomic diffusion via the addition of an oxide and the resultant lowering of the ordering temperature. Effect (1) was observed in the case of SiO₂ addition, effect (2) was generally observed in the case of oxide addition and the RTA process, and effect (3) was prominent in the case of ZnO addition. With the addition of ZnO, the L1₀ ordering started at below 400 °C and was completed at 500 °C. Finally, dot patterns were successfully fabricated down to a diameter of 15 nm using electron beam lithography, and the magnetic state of the dot pattern was observed by magnetic force microscopy.